CN108448119A - Flexible fiber shape lithium-carbon dioxide battery of low charging voltage and preparation method thereof - Google Patents
Flexible fiber shape lithium-carbon dioxide battery of low charging voltage and preparation method thereof Download PDFInfo
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- CN108448119A CN108448119A CN201810201452.4A CN201810201452A CN108448119A CN 108448119 A CN108448119 A CN 108448119A CN 201810201452 A CN201810201452 A CN 201810201452A CN 108448119 A CN108448119 A CN 108448119A
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- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of flexible fiber shape lithium carbon dioxide batteries of low charging voltage, and the structure composition of battery from inside to outside is lithium metal silk, gel electrolyte, working electrode, porous heat-shrink tube respectively.The invention also discloses a kind of preparation methods of the flexible fiber shape lithium carbon dioxide battery of low charging voltage.The invention has the advantages that, device charged electric potential significantly can be reduced to about 3.4V by the flexible fiber shape lithium carbon dioxide battery of obtained low charging voltage, and synthesis material is cheap and easy to get, working electrode preparation is simple, device packaging technology is concisely quick, is suitable for batch production, has a extensive future.
Description
Technical field
The present invention relates to a kind of batteries and preparation method thereof, and in particular to a kind of flexible fiber shape lithium-of low charging voltage
Carbon dioxide battery and preparation method thereof belongs to metal-air battery field.
Background technology
With the fast development of World Science technology, the power density and energy density of conventional lithium ion battery more cannot
Meets the needs of mankind use Portable movable electronic equipment for a long time, it is a kind of close with superenergy that people are badly in need of exploitation
It spends and safe and reliable novel battery system substitutes current commercialization lithium battery, week is used significantly to extend electronic equipment
Phase improves people’s lives and working efficiency.
Lithium-carbon dioxide battery is one of the novel battery system with ultra high energy density developed in recent years.
It react the principle of generation lithium carbonate and simple substance carbon by chemical energy under the action of catalyst using carbon dioxide gas and lithium ion
Electric energy is converted into power for dispatch from foreign news agency pipeline equipment.Currently, the research and development of lithium-carbon dioxide battery still belong to the ground zero stage, it is only limited
Different materials be proven to have catalytic activity, including carbon nanotube (Chem.Commun., 2015,51,14636-
14639), modified graphene (Angew.Chem., 2015,127,6650~6653), section's qin carbon black (Energy
Environ.Sci., 2014,7,677~681) carbon materials such as；Carbon nanotube is received by its better cyclical stability
More widely uses and study.But in actual use, the current potential basic bit that carbon nanometer pipe catalytic lithium carbonate decomposes
Between 4.2~4.5V, electrolyte can be decomposed gradually under such high potential, and electrode material carbon nanotube itself is also easy
By Oxidative demage, lead to battery performance rapid decay until failing, while being accompanied by some safety problems.Therefore, in order to
Energy content of battery efficiency and working life are improved, some active material urgent needs with low charged electric potential are developed and are applied to the body
In system, such as rare earth metal ruthenium Ru (Joule, 2017,1,1359~370), molybdenum carbide Mo2C(Adv.Funct.Mater.,2017,
1700564).In addition, being worth it is emphasized that present lithium-carbon dioxide cell gas electrode research also focuses on substantially
Powder body material, when use, which generally requires to be made into slurry, to be coated on the collectors such as carbon paper, nickel foam, and button battery is placed in
In tested, such air electrode is difficult to realize lightweight and flexibility, is not suitable for being assembled into scale power supply device.
In terms of practical application, traditional two-dimensional rigid plane battery cannot meet wearable electronic to cell flexible and can respiratory
Requirement, and designing cells into one dimension fibre shape configuration will so that it has the ability that can weave, and can preferably deform and breathe freely,
Meet design requirement of the wearable electronic in terms of ergonomics.
High-conductivity carbon nanotube film has excellent flexibility and higher conductivity, is a kind of ideal soap-free emulsion polymeization
Agent, self-supporting lithium-carbon dioxide battery air electrode matrix.By molybdenum carbide and High-conductivity carbon nanometer with more high catalytic activity
Pipe film be combined prepare a kind of carbon nanotube self-supporting laminated film of uniform load molybdenum carbide nano particle not only can be with
Charged electric potential is effectively reduced, and is conducive to simplify flexible fiber shape lithium-carbon dioxide battery device construction technology, promotes battery
Practical application potentiality.
Invention content
The object of the present invention is to provide a kind of flexible fiber shape lithium-carbon dioxide battery of low charging voltage and preparation sides
Method.The flexible fiber shape lithium-carbon dioxide battery have lower initiation of charge voltage (3.4V), good chemical property and
Excellent deformability, synthesis material is cheap and easy to get, working electrode preparation is simple, device packaging technology is concisely quick, is suitable for
Batch production, has a extensive future.
The present invention is to be realized by the following technical programs：
A kind of flexible fiber shape lithium-carbon dioxide battery of low charging voltage, the working electrode of the battery is by highly conductive
The two molybdenum carbon nano-particles loaded on carbon nano-tube film and carbon nano tube surface in the film are constituted.Wherein, height is led
The thickness of electrical carbon nano-tube film is 5~30um, a diameter of 10~500nm of single-root carbon nano-tube；Single two molybdenums carbon nanometer
The size of grain is 1~300nm；In the laminated film, the mass percent of two molybdenum carbon and carbon nanotube is:(0.1~
0.9):The quality of (0.9~0.1), laminated film unit area is 0.2~2mg/cm2。
The flexible fiber shape lithium-structure composition of carbon dioxide battery from inside to outside of the low charging voltage is lithium metal respectively
Silk, gel electrolyte, working electrode, porous heat-shrink tube.Wherein, a diameter of 2.8~3.4mm of lithium metal silk, length be 1~
1000mm；Gel electrolyte is directly adhered to and is wrapped on lithium metal silk, and thickness is 0.01~10mm；Working electrode is load two
The carbon nano-tube coextruded film of molybdenum carbon nano-particle；The porous a diameter of 3.8~4.5mm of heat-shrink tube, length are 1~1000mm,
The size of single hole is 0.1~2mm in tube wall, and distribution density is 1~30/cm2。
Further, one end of the lithium metal silk is fixed with metal copper conductor.
The present invention also provides the preparation methods of flexible fiber shape lithium-carbon dioxide battery of low charging voltage.
The preparation method of flexible fiber shape lithium-carbon dioxide battery of low charging voltage, includes the following steps：
(1) is mixed into molybdenum source with one or both of ammonium molybdate, sodium molybdate, is electricity with high-conductivity carbon nanotube film
The quality and molybdenum source of the mixed solution of pole matrix, the mixed solution of addition deionized water and ethylene glycol, deionized water and ethylene glycol
Mass ratio with electrode matrix gross mass is (50~360):1；In the mixed solution of deionized water and ethylene glycol, water and ethylene glycol
Volume ratio be 1:(1.5~2.5), are sufficiently stirred and ultrasound is until molybdenum source is completely dissolved, and high-conductivity carbon nanotube film is complete
It infiltrates in mixed solution.
(2) mixture made from step (1) is transferred in the counteracting tank that liner is polytetrafluoroethylene (PTFE) by, is placed in constant temperature
Hydro-thermal reaction is carried out in drying box：160~220 DEG C are warming up to the heating rate of 1~20 DEG C/min, 5~25h of heat preservation carries out water
It is thermally grown, cooled to room temperature after reaction.Counteracting tank is opened, film is taken out from mixed solution, uses deionized water
Rinsing is placed on dry in -10~-60 DEG C of freeze drier repeatedly, after moisture completely removes, obtains laminated film A.
(3) the laminated film A that step (2) obtains is laid in Noah's ark by, is placed in tube furnace flat-temperature zone and is calcined：With
N2, He and Ar a kind of gas or mixed gas as inert gas source, be first that 200~400ml/min is passed through inertia with flow
Gas 10~30 minutes is to exclude air；It is passed through H again2/ Ar mixed gas (H in gaseous mixture2Shared volume is 3~10%), mixing
Total gas flow rate is fixed as 50~400ml/min, and 700~900 DEG C are warming up to the heating rate of 1~20 DEG C/min, and heat preservation 1~
4h is converted, and cools to room temperature with the furnace after reaction, you can the carbon nanotube for obtaining two molybdenum carbon nano-particles of load is multiple
Close film.
(4) is in O2And H2O content is below in the glove box of 1ppm, by double trifluoromethanesulfonimide lithiums, tetraethylene glycol
Dimethyl ether is with (2.8~3.2):The mass ratio of (1.8~2.2) is configured to solution X, by polyvinylidene fluoride-hexafluoropropene, N first
Base pyrrolidones is with (0.8~1.2):The mass ratio of (3.8~4.2) is configured to solution Y, by 2- hydroxy-2-methyl -1- phenyl -
1- acetone, ethoxylated trimethylolpropane triacrylate are with 1:The mass ratio of (298~302) is configured to solution Z；By solution
X, solution Y and solution Z are with (3.8~4.2):(4.8~5.2):After the mass ratio of (2.8~3.2) is mixed and is sufficiently stirred, obtain
Thick mixed solution M.
(5) is in glove box, the glass for being 3.5~4.5mm by the thick mixed solution M obtained in step 4 injection internal diameters
In glass pipe, takes one end to fix the lithium metal silk of upper metal copper conductor, a diameter of 2.8~3.4mm, be inserted into the glass tube fully
After lifting picks thick mixed solution M, take out the lithium silk, with wavelength be 365nm ultraviolet light uniform irradiation 10~30 seconds after,
The lithium metal silk for being coated with gel electrolyte is made.
(6) is in glove box, the carbon nano-tube coextruded film for the two molybdenum carbon nano-particle of load that step (3) is obtained
It is carefully wrapped on the lithium metal silk for be coated with gel electrolyte until the entire gel electrolyte of covering, is being fixed with metallic copper
The other end of the lithium silk of conducting wire fixes another metallic copper from the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load
After conducting wire, which is inserted in the porous heat-shrink tubes of a diameter of 3.8~4.5mm, the heat for being 100~200 DEG C with temperature
Air pressure gun uniformly purges, and heat-shrink tube is made to shrink to fix and the packaged device.The linear unit is sealed to taking-up from glove box,
It can be obtained flexible fiber shape lithium-carbon dioxide battery of low charging voltage.
The present invention has the following advantages：
The present invention is prepared for the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load using raw material cheap and easy to get
And flexible fiber shape lithium-carbon dioxide battery of low charging voltage has been constructed using it, manufacturing cost is cheap, reaction process letter
Single, process controllability is strong.Two synthesized molybdenum carbon nano-particle grain sizes are tiny, size uniformity, and dispersibility is preferable, with carbon nanometer
Pipe combines firm, has good chemical property when the combination electrode is used for lithium-carbon dioxide anode, can effective handle
Initiation of charge voltage drop is as low as 3.5V or less.Meanwhile using the carbon nano-tube coextruded film of the two molybdenum carbon nano-particle of load
Have excellent flexibility as fibrous lithium-carbon dioxide battery constructed by working electrode, it can be in various large deformation conditions
Lower normal work.
Description of the drawings
Fig. 1 is the SEM photograph of high-conductivity carbon nanotube film used in the embodiment of the present invention 1.It can be apparent from the figure
Find out the distribution situation of carbon nanotube and its caliber and size in the high-conductivity carbon nanotube film.
Fig. 2 is high-conductivity carbon nanotube film used in the embodiment of the present invention 1 separately as lithium-carbon dioxide battery gas
Charging and discharging curve figure when body electrode.From the figure it is obvious that the discharge voltage of electrode is about 2.8V, charging voltage is about
4.2V。
Fig. 3 is the XRD diagram of the carbon nano-tube coextruded film of the two molybdenum carbon nano-particles of load obtained of the embodiment of the present invention 1
Spectrum.It can clearly determine that the laminated film is only made of two molybdenum carbon and simple substance carbon from the figure, be free of other impurities phase.
Fig. 4 is the low power of the carbon nano-tube coextruded film of the two molybdenum carbon nano-particles of load obtained of the embodiment of the present invention 1
SEM photograph.From the figure this it appears that being carried on two molybdenum carbon nano-particles of carbon nano tube surface in laminated film
Distribution situation.
Fig. 5 is the high power of the carbon nano-tube coextruded film of the two molybdenum carbon nano-particles of load obtained of the embodiment of the present invention 1
SEM photograph.From the figure this it appears that be carried on two molybdenum carbon nano-particles of carbon nano tube surface size and
The combination situation of itself and carbon nanotube matrix.
Fig. 6 is that the carbon nano-tube coextruded film of the two molybdenum carbon nano-particles of load obtained of the embodiment of the present invention 1 is applied to
Charging and discharging curve figure when lithium-carbon dioxide cell gas electrode.It can be, it is evident that the discharge voltage of electrode be maintained at from the figure
Near 2.8V, and charging voltage is then significantly reduced to 3.4V.
Fig. 7 is the carbon nano-tube coextruded film obtained to load two molybdenum carbon nano-particles of the embodiment of the present invention 1 as gas
Body electrode and the exterior appearance optics picture and the battery of low charging voltage flexible fiber shape lithium-carbon dioxide battery constructed
Overall structure diagram.The threadiness battery device can be clearly apparent from inside to outside respectively by lithium metal silk, gel from the figure
Electrolyte, working electrode and porous heat-shrink tube composition.
Fig. 8 is the carbon nano-tube coextruded film obtained to load two molybdenum carbon nano-particles of the embodiment of the present invention 1 as gas
Body electrode and optics that low charging voltage flexible fiber shape lithium-carbon dioxide battery for constructing works under the conditions of differently curved shines
Piece.It can be seen from the figure, which has excellent flexibility, can be worked normally under the conditions of various modifications.
Fig. 9 is the carbon nano-tube coextruded film obtained to load two molybdenum carbon nano-particles of the embodiment of the present invention 1 as gas
Body electrode and optical photograph that low charging voltage flexible fiber shape lithium-carbon dioxide battery for constructing is LED light power supply for a long time.
It can be seen from this figure that the battery can be LED light power supply at least 12h, confirm that it is close with higher energy to a certain extent
Degree.
Specific implementation mode
The particular content of the present invention is described as follows with reference to specific embodiment：
Embodiment 1
It weighs 180mg ammonium molybdates to be added in 10ml deionized waters, with the magnetic stirring apparatus of mixing speed 300r/min, stirring
Wiring solution-forming is dissolved, 20ml ethylene glycol is measured again later and is added in above-mentioned solution, then stirred with the magnetic force of mixing speed 300r/min
Device stirring 30min is mixed, so that component is uniformly mixed, obtains mixed solution A.It is about 15 μm to take thickness, width 10mm, and length is
The high-conductivity carbon nanotube film of 100mm is placed in mixed solution A, is the ultrasonic device ultrasound 30min of 400W with power, height is made to lead
Electrical carbon nano-tube film complete wetting is in mixed solution A.After the completion of ultrasound, by said mixture be transferred to capacity be 50ml with
Polytetrafluoroethylene (PTFE) be liner counteracting tank in and be sealed, as in thermostatic drying chamber, heated up with the heating rate of 10 DEG C/min
To 200 DEG C, heat preservation 10h carries out hydro-thermal reaction, after reaction with babinet cooled to room temperature.Counteracting tank is opened, by film
It is taken out from mixed solution, rinses 6 times repeatedly with deionized water and be placed on drying in -50 DEG C of freeze drier, wait for that moisture is complete
After full removal, laminated film A is obtained.Dried laminated film A is placed in Noah's ark, Noah's ark is put into tube furnace, is passed through
The Ar inert gases of 200ml/min exclude air, then are passed through the H that flow is 200ml/min2The H that volume fraction is 5%2/ Ar is mixed
It closes gas and 800 DEG C of temperature is warming up to the heating rate of 10 DEG C/min, heat preservation 2h carries out conversion reaction, closes after reaction
Close H2/ Ar mixed gas is cooled to room temperature under pure Ar atmosphere protections, obtains the carbon nanotube of two molybdenum carbon nano-particles of load
Laminated film.In the laminated film, two molybdenum carbon nano-particles are evenly distributed on carbon nano tube surface, and close with carbon nanotube
Set；Wherein, a diameter of 30~60nm of carbon nanotube, the grain sizes of two molybdenum carbon nano-particles are 5~50nm, two molybdenum carbon with
The mass percent of carbon nanotube is about 0.3:0.7, laminated film thickness is about 15 μm, and the quality of unit area is about 0.8mg/
cm2。
Take 1cm2The carbon nano-tube coextruded film for loading two molybdenum carbon nano-particles, with the TEGDME solution of 1M LiTFSI
Lithium-carbon dioxide button cell, the charge and discharge under the current density of 100mA/g is made using lithium piece as anode as electrolyte
The charging voltage of battery significantly can be reduced to about 3.4V, as shown in Figure 6 by electricity.
In O2And H2O content is below in the glove box of 1ppm, takes double trifluoromethanesulfonimide lithium 2.4g, tetraethylene glycol
Dimethyl ether 1.6g is configured to solution X, and polyvinylidene fluoride-hexafluoropropene 1.0g, N methyl pyrrolidone 4.0g is taken to be configured to solution
Y takes 2- hydroxy-2-methyl -1- phenyl -1- acetone 0.01g, ethoxylated trimethylolpropane triacrylate 3.0g to be configured to
Solution Z；Solution X and solution Z are all added to after being adequately mixed stirring in solution Y, obtain thick mixed solution M.It will
In the glass tube that thick mixed solution M injections internal diameter is 3.9mm, one end is taken to fix upper metal copper conductor, a diameter of 3.2mm,
The lithium metal silk that length is about 8cm, be inserted into the glass tube fully lifting pick thick mixed solution M after, take out the lithium silk,
The 15 seconds curing gel electrolyte of ultraviolet light uniform irradiation for being 365nm with wavelength, takes 8cm again later2The laminated film prepared
It is carefully wrapped on the lithium metal silk for be coated with gel electrolyte until covering entire gel electrolyte.It is led being fixed with metallic copper
The other end of the lithium silk of line is fixed another metallic copper and is led from the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load
After line, which is inserted in the porous heat-shrink tubes of a diameter of 4mm, the heat gun for being 150 DEG C with temperature uniformly purges, and makes
Heat-shrink tube shrinks to fix and the packaged device.The linear unit is sealed to taking-up from glove box, is placed in pure titanium dioxide
In carbon atmosphere, you can obtain flexible fiber shape lithium-carbon dioxide battery of low charging voltage.The battery has excellent flexible
Property, it can be worked normally under the conditions of various modifications, as shown in Figure 8；The battery also has higher energy density simultaneously, can be
LED light power supply at least 12h, as shown in Figure 9.
The overall structure such as attached drawing of the flexible fiber shape lithium-carbon dioxide battery for the low charging voltage that the application is prepared
Shown in 7, it can be seen that flexible fiber shape lithium-carbon dioxide battery of low charging voltage from inside to outside respectively by lithium metal silk 4,
Gel electrolyte 3, working electrode 2 and porous heat-shrink tube 1 form, and metal copper conductor 5 is fixed in one end of lithium metal silk 4.
Embodiment 2
It weighs 90mg ammonium molybdates to be added in 8ml deionized waters, with the magnetic stirring apparatus of mixing speed 200r/min, stirring is molten
Wiring solution-forming is solved, 25ml ethylene glycol is measured again later and is added in above-mentioned solution, then with the magnetic agitation of mixing speed 300r/min
Device stirs 30min, so that component is uniformly mixed, obtains mixed solution A.It is about 20 μm to take thickness, width 6mm, length 80mm
High-conductivity carbon nanotube film be placed in mixed solution A, be the ultrasonic device ultrasound 30min of 400W with power, make High-conductivity carbon
Nano-tube film complete wetting is in mixed solution A.After the completion of ultrasound, by said mixture be transferred to capacity be 50ml with poly- four
Vinyl fluoride be liner counteracting tank in and be sealed, as in thermostatic drying chamber, 180 are warming up to the heating rate of 5 DEG C/min
DEG C, heat preservation 20h carries out hydro-thermal reaction, after reaction with babinet cooled to room temperature.Counteracting tank is opened, by film from mixing
It is taken out in solution, rinses 6 times repeatedly with deionized water and be placed on drying in -50 DEG C of freeze drier, wait for that moisture completely removes
Afterwards, laminated film A is obtained.Dried laminated film A is placed in Noah's ark, Noah's ark is put into tube furnace, 300ml/ is passed through
The Ar inert gases of min exclude air, then are passed through the H that flow is 200ml/min2The H that volume fraction is 5%2/ Ar mixed gas,
And 750 DEG C of temperature is warming up to the heating rate of 10 DEG C/min, heat preservation 4h carries out conversion reaction, closes H after reaction2/Ar
Mixed gas is cooled to room temperature under pure Ar atmosphere protections, obtains the carbon nanotube THIN COMPOSITE of two molybdenum carbon nano-particles of load
Film.
In O2And H2O content is below in the glove box of 1ppm, takes double trifluoromethanesulfonimide lithium 2.5g, tetraethylene glycol
Dimethyl ether 1.5g is configured to solution X, and polyvinylidene fluoride-hexafluoropropene 0.9g, N methyl pyrrolidone 4.1g is taken to be configured to solution
Y takes 2- hydroxy-2-methyl -1- phenyl -1- acetone 0.02g, ethoxylated trimethylolpropane triacrylate 3.1g to be configured to
Solution Z；Solution X and solution Z are all added to after being adequately mixed stirring in solution Y, obtain thick mixed solution M.It will
In the glass tube that thick mixed solution M injections internal diameter is 3.9mm, one end is taken to fix upper metal copper conductor, a diameter of 3.0mm,
The lithium metal silk that length is about 6cm, be inserted into the glass tube fully lifting pick thick mixed solution M after, take out the lithium silk,
The 20 seconds curing gel electrolyte of ultraviolet light uniform irradiation for being 365nm with wavelength, takes 4.8cm again later2The THIN COMPOSITE prepared
Film is carefully wrapped on the lithium metal silk for be coated with gel electrolyte until covering entire gel electrolyte.It is being fixed with metallic copper
The other end of the lithium silk of conducting wire fixes another metallic copper from the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load
After conducting wire, which is inserted in the porous heat-shrink tubes of a diameter of 3.9mm, the heat gun for being 200 DEG C with temperature is uniformly blown
It sweeps, heat-shrink tube is made to shrink to fix and the packaged device.The linear unit is sealed to taking-up from glove box, is placed in pure two
In carbonoxide atmosphere, you can obtain flexible fiber shape lithium-carbon dioxide battery of low charging voltage.
Embodiment 3
It weighs 70mg ammonium molybdates to be added in 10ml deionized waters, with the magnetic stirring apparatus of mixing speed 200r/min, stirring
Wiring solution-forming is dissolved, 25ml ethylene glycol is measured again later and is added in above-mentioned solution, then stirred with the magnetic force of mixing speed 300r/min
Device stirring 30min is mixed, so that component is uniformly mixed, obtains mixed solution A.It is about 20 μm to take thickness, width 10mm, and length is
The high-conductivity carbon nanotube film of 80mm is placed in mixed solution A, is the ultrasonic device ultrasound 30min of 400W with power, height is made to lead
Electrical carbon nano-tube film complete wetting is in mixed solution A.After the completion of ultrasound, by said mixture be transferred to capacity be 50ml with
Polytetrafluoroethylene (PTFE) be liner counteracting tank in and be sealed, as in thermostatic drying chamber, heated up with the heating rate of 10 DEG C/min
To 220 DEG C, heat preservation 8h carries out hydro-thermal reaction, after reaction with babinet cooled to room temperature.Open counteracting tank, by film from
It is taken out in mixed solution, rinses 6 times repeatedly with deionized water and be placed on drying in -50 DEG C of freeze drier, wait for that moisture is complete
After removal, laminated film A is obtained.Dried laminated film A is placed in Noah's ark, Noah's ark is put into tube furnace, is passed through
The Ar inert gases of 150ml/min exclude air, then are passed through the H that flow is 200ml/min2The H that volume fraction is 5%2/ Ar is mixed
It closes gas and 800 DEG C of temperature is warming up to the heating rate of 10 DEG C/min, heat preservation 1.5h carries out conversion reaction, after reaction
Close H2/ Ar mixed gas is cooled to room temperature under pure Ar atmosphere protections, obtains the carbon nanometer of two molybdenum carbon nano-particles of load
Pipe laminated film.
In O2And H2O content is below in the glove box of 1ppm, takes double trifluoromethanesulfonimide lithium 2.3g, tetraethylene glycol
Dimethyl ether 1.7g is configured to solution X, and polyvinylidene fluoride-hexafluoropropene 0.1g, N methyl pyrrolidone 4.1g is taken to be configured to solution
Y takes 2- hydroxy-2-methyl -1- phenyl -1- acetone 0.02g, ethoxylated trimethylolpropane triacrylate 3.0g to be configured to
Solution Z；Solution X and solution Z are all added to after being adequately mixed stirring in solution Y, obtain thick mixed solution M.It will
In the glass tube that thick mixed solution M injections internal diameter is 4.1mm, one end is taken to fix upper metal copper conductor, a diameter of 3.2mm,
The lithium metal silk that length is about 8cm, be inserted into the glass tube fully lifting pick thick mixed solution M after, take out the lithium silk,
The 15 seconds curing gel electrolyte of ultraviolet light uniform irradiation for being 365nm with wavelength, takes 8cm again later2The laminated film prepared
It is carefully wrapped on the lithium metal silk for be coated with gel electrolyte until covering entire gel electrolyte.It is led being fixed with metallic copper
The other end of the lithium silk of line is fixed another metallic copper and is led from the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load
After line, which is inserted in the porous heat-shrink tubes of a diameter of 4.0mm, the heat gun for being 100 DEG C with temperature uniformly purges,
Heat-shrink tube is set to shrink to fix and the packaged device.The linear unit is sealed to taking-up from glove box, is placed in pure dioxy
Change in carbon atmosphere, you can obtain flexible fiber shape lithium-carbon dioxide battery of low charging voltage.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (3)
1. a kind of flexible fiber shape lithium-carbon dioxide battery of low charging voltage, which is characterized in that the structure of battery from inside to outside
Composition is lithium metal silk, gel electrolyte, working electrode, porous heat-shrink tube respectively；Wherein, a diameter of the 2.8 of lithium metal silk~
3.4mm, length are 1~1000mm；Gel electrolyte is directly adhered to and is wrapped on lithium metal silk, and thickness is 0.01~10mm；
Working electrode is the carbon nano-tube coextruded film for loading two molybdenum carbon nano-particles, and thickness is 5~30um, the laminated film
In, the size of a diameter of 10~500nm of single-root carbon nano-tube, single two molybdenums carbon nano-particle are 1~300nm, two molybdenums
The mass percent for changing carbon and carbon nanotube is:(0.1~0.9):The quality of (0.9~0.1), laminated film unit area is
0.2~2mg/cm2；The porous a diameter of 3.8~4.5mm of heat-shrink tube, length are 1~1000mm, the size of single hole in tube wall
For 0.1~2mm, distribution density is 1~30/cm2。
2. flexible fiber shape lithium-carbon dioxide battery of low charging voltage according to claim 1, which is characterized in that described
One end of lithium metal silk is fixed with metal copper conductor.
3. the preparation method of flexible fiber shape lithium-carbon dioxide battery of low charging voltage as claimed in claim 1 or 2, special
Sign is to include the following steps：
(1) is mixed into molybdenum source with one or both of ammonium molybdate, sodium molybdate, using high-conductivity carbon nanotube film as electrode base
The quality and molybdenum source and electricity of the mixed solution of body, the mixed solution of addition deionized water and ethylene glycol, deionized water and ethylene glycol
The mass ratio of pole matrix gross mass is (50~360):1；In the mixed solution of deionized water and ethylene glycol, the body of water and ethylene glycol
Product is than being 1:(1.5~2.5), be sufficiently stirred and ultrasound until molybdenum source be completely dissolved, high-conductivity carbon nanotube film complete wetting
Into mixed solution；
(2) mixture made from step (1) is transferred in the counteracting tank that liner is polytetrafluoroethylene (PTFE) by, is placed in freeze-day with constant temperature
Hydro-thermal reaction is carried out in case：160~220 DEG C are warming up to the heating rate of 1~20 DEG C/min, 5~25h of heat preservation carries out hydro-thermal life
It grows, after reaction cooled to room temperature；Counteracting tank is opened, film is taken out from mixed solution, repeatedly with deionized water
Rinsing is placed on drying in -10~-60 DEG C of freeze drier, after moisture completely removes, obtains laminated film A；
(3) the laminated film A that step (2) obtains is laid in Noah's ark by, is placed in tube furnace flat-temperature zone and is calcined：With N2、He
A kind of gas or mixed gas with Ar is first that 200~400ml/min is passed through inert gas 10 with flow as inert gas source
~30 minutes to exclude air；It is passed through H again2/ Ar mixed gas (H in gaseous mixture2Shared volume is 3~10%), mixed gas is total
Flow is fixed as 50~400ml/min, is warming up to 700~900 DEG C with the heating rate of 1~20 DEG C/min, 1~4h of heat preservation is carried out
Conversion, cools to room temperature with the furnace after reaction, you can obtains the carbon nano-tube coextruded film of two molybdenum carbon nano-particles of load；
(4) is in O2And H2O content is below in the glove box of 1ppm, by double trifluoromethanesulfonimide lithiums, tetraethylene glycol diformazan
Ether is with (2.8~3.2):The mass ratio of (1.8~2.2) is configured to solution X, by polyvinylidene fluoride-hexafluoropropene, N methyl pyrroles
Pyrrolidone is with (0.8~1.2):The mass ratio of (3.8~4.2) is configured to solution Y, by 2- hydroxy-2-methyl -1- phenyl -1- third
Ketone, ethoxylated trimethylolpropane triacrylate are with 1:The mass ratio of (298~302) is configured to solution Z；By solution X, molten
Liquid Y and solution Z are with (3.8~4.2):(4.8~5.2):After the mass ratio of (2.8~3.2) is mixed and is sufficiently stirred, obtain sticky
Shape mixed solution M；
(5) is in glove box, the glass tube for being 3.5~4.5mm by the thick mixed solution M obtained in step 4 injection internal diameters
In, it takes one end to fix the lithium metal silk of upper metal copper conductor, a diameter of 2.8~3.4mm, is inserted into the glass tube and fully lifts
After picking thick mixed solution M, take out the lithium silk, with wavelength be 365nm ultraviolet light uniform irradiation 10~30 seconds after, be made
It is coated with the lithium metal silk of gel electrolyte；
(6) in glove box, the carbon nano-tube coextruded film for the two molybdenum carbon nano-particle of load that step (3) is obtained is careful
Ground is wrapped on the lithium metal silk for be coated with gel electrolyte until the entire gel electrolyte of covering, is being fixed with metal copper conductor
Lithium silk the other end, from load two molybdenum carbon nano-particles carbon nano-tube coextruded film on fix another metal copper conductor
Afterwards, which is inserted in the porous heat-shrink tubes of a diameter of 3.8~4.5mm, the heat gun for being 100~200 DEG C with temperature
Uniformly purging makes heat-shrink tube shrink to fix and the packaged device；The linear unit is sealed to taking-up from glove box, you can
Obtain flexible fiber shape lithium-carbon dioxide battery of low charging voltage.
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Application publication date: 20180824 |